Production of yellow dye images by color development



Patented Sept. 19, 1950 PRODUCTION OF YELLOW DYEIMAGESBY.

COLOR DEVELOPMENT Donald E. Sargent and Robert, Guntherg, Easton, Pa., assignors 19030118131, Aniline1 &' Film Corporation, New York, big-Y m cor-poretion of Delaware No Drawing. ApplicationDecember fl,1M8;

Serial No. 66,825:

The present invention relates; to the preparation of yellow dye images by photographic color forming development.

One of the classic methods for the production of dyestuff images in photographic elements involves the incorporation in a monopack of nondiffusing color formers, the exposure of the monopack and the-development therein orthe desired subtractive color images by color development: with a primary aromatic amino developer of the l rial No. 640,382, now-Patent No. 2,486,440; No

vember 1, 1949, describe the production of azine dye images by the color development of an exposed silver halide emulsion with a, 2.4-diamino- 8 Claims. (01. ashes)? 7 Such lack of success in synthesizing theiyellow dye. image by color development, materially op.er ated; against the? adoption of this; procession practical use despite he: exc llen e of the; dye

- Producedt l rthe reaso that its ad ption woii d r quire as nseharatelfr ms th t. 0t olor f rming development of the cyan and magenta to insure the formation at apermanent ye image.

We have now discovered, very surprisingly indeed, that a permanent'yel'low dye image can be produced simultaneously with the cyan and maenta azine dye images by color forming development with a 2.4-diamirxo aniline in the presence of a keto methylene compound providing that the pH of the photographic element subaniline in the presence of a colon former which is preferably an aromatic compound containing at least one hydroxyl, group linked to the aromatic structure. This process! has as its greatest merit the fact that it yields dyestuif images whichrare;much moreistable, particularly o acid a vapors, than are, the; azomethines 0r quinonie mines.

However, suchiprocess as developed to the present time did not lend itself, to the processing of multilayer film with the same simplicity as the a older method, primarily because of the inability of operators to, effectively produce a permanent yellow dye image simultaneously with magenta and cyan dye images upon color development. As stated the color formers generally employed in the azine method: were of the phenolic type,

and these invariably leditothe formation ofazined jected to processing be adjusted with an alkali in alii al phase of. he process on ratie suntil a yellow image clearly manifestsitselfl j It is an object ofthepresent invention to color develop a developablesilverhalide emulsion with a 2.4-diaminoaniline in the presence of a keto methylene compound to produce a yellow dye image.

It is a further object of the present invention to color-develop a developable silver halide emulsion with a zA-diaminoi aniline in the presence of a keto methylene compound while adjusting the pH by means of analkali in a final phase of the processing operation until a yellowimage manifests itself-1 Other and further objects of the invention will become apparent asthe= description proceeds.

The color forming developers which we employ, and which as stated are, of"the 2.4-diaminoaniline type, maybe represented by the following structural formula:

the like, hydroxy alkyll-such as hydroxy ethyl,

hydroxy propyl and the like, sulfo alkyl such as sulfomethyl, sulfopropyl, sulfobutyl and the like, or an aromatic radical such as aryl, i. e., phenyl, naphthyl and the like, carboxy aryl, i. e., carboxy phenyl, carboxy naphthyl and the like, sulfo aryl, i. e., sulfophenyl, sulfonaphthyl and the like, alkoxy aryl such as methoxy phenyl, methoxy naphthyl, ethoxy phenyl, butyroxy phenyl and the like, alkyl aryl such as toluyl, ethylphenyl, propylphenyl and the like, carboxy alkylaryl, such as carboxy methyl phenyl, carboxy' ethyl phenyl and the like, carboxy alkoxy aryl, such as carboxy methoxy phenyl, carboxy ethoxy phenyl, hydroxy alkyl aryl such as hydroxy methyl phenyl, hydroxy ethyl phenyl and the like, and hydroxy a1- koxy aryl such as hydroxy methoxy phenyl, hydroxy ethoxy phenyl and the like, R is an aromatic or aliphatic radicalasillustrated above, and X and Y are hydrogen, alkyl as above, sulfo, or carboxy. Preferably the compounds which are utilized are the N-substituted-l.G-diamino v metanilic acids, in which case Y is hydrogen, and

H NUaH H NOaHl 2. 6 (N sulfomethyl N phenyl) amino- 4-phenylamino-metanilic acid;

00H; QHiSOaH 3. 2.4-bis(3'-carboxyphenylamino)aniline.

coon

. OOOH 4. 4.6-bis-(phenylamino) -n ietanilic acid.

m roon,

5. 4.6-bis-(4-methoxypheny1amino)-metani1ic 6. 4 (2 methoxyphenylamino) 6 (4- methoxyphenylamino) -metanilic acid.

HOaS- 7. 4-(4'-methoxypyhenylamino) 6 (phenylamino) -metanilic acid.

HOaS- 8. 4.6- bis(2'-methoxyphenylamino) -metani1ic acid.

NM: 0 CHI 9. 4-(3 -carboxyphenylamino)-6-(4'-methoxyphenylamino) -metanilic acid;

HOaS- COOH 10. 4-(3'-carboxy 4 methoxyphenylamino) 6- (4'-methoxyphenylamino) -metani1ic acid.

11 Boas-O 11. 4-(4-sulfophenylamino) 6 y-methoxy phenylamino) -metanilic acid.

H N O CH;

HOaS- 12.2.4 -Bi s (phenyiaminoi 5 amino benzoic 19. 2.4 di (4' methox y phenyianunoi 5 1 acid. aminobenzoic acid. 1

1% OOH HOOO- f g OCH NH:

13. 4 (4' methoxyphenylamino) s (N m1, carboxymethyl N phenylamino) metanilic acid. 1

. 1 2.4 di (phenylamino) -5 --aminoto1ucne- 15 w-SUlfOIliC acid.

-N--ocm 2o Hmsmc- I IH: H 14. 4 (4' sulfophenylamino) s (N car I boxymethyl N 4' methoxyphenylamino) L metanilic acid.

CH;O---]NCHOQOH 21. 4.6-di-(methy1amino) -metani1ic acid.

H013 H i 3 H N-OSO|H I NH Boas- E 15. 4-(2-pyridy1amino)-6-(N-carboxymethy1- NOE: N-4'-methoxy-phenyl-amino)-metani1ic acid. m

CHaO -NCH2COOH m 22. 4 phenylamino 6 methylamino me- 0 tanilic acid.

NOH 16. 4 (4' methoxyphenylamino) 6 dimethylaminometanilic acid.

H The color former which is utilized for the for- H2 mation of the yellow dye image upon development is any open chain keto methylene compound, i. e., any compound containing in a straight chain a methylene group which is activated by one or more keto groups or by a keto group and a cyano or SO2 group.

17. 4 (4 sulfophenylamino) 6 di methylaminometanilic acid.

B as- Examples of such compounds are:

H 1. Acetoacetanilide. -N-C -s0.H 2. N-1-naphthy1acetoacetamide. 3. N-1-naphthy1-a-benzoylacetamide. 4. N.N'-ethylenebisacetoacetamide 18. 4- (4'-methoxypheny1amino) -6- (4-methy1- pbellylaminm 'metanilic acid- CH3cocmcomacnzcnmncocmcocm a CH. I 5. N.N -ethylenebis-a-benaoy1acetam1de. 503$ 6. p.p'-Bi-o-acetoacetanislde H D CHI omcoomc ONH E ONHC 0011.00011- lira, 5" 1 on. com

'7. N-2enaphthy1benzoylacetamide. 22. 2 p benzoylacetamidobenzamido--stea- 8. p.p-Biacetoacetanilide. roylamino-p-toluene-sulfonic acid. r 9. p.p-Bi-a-benzoylacetanilide. CH3 NHCOOnHu 10. M'- Terephtha1oylbis-(3 -ch1oro-4.6 -dimethoxy-acetanilide). 5 OOOGHNHOCO'NH OCHa (H;

. 11. M -Terephtha.1oy1bis-(4-ch1oro-5-methy1- acetaniside) 23. m.-Terephtha1oy1bisacetanilide.

24. 4.4-methylenebisacetoacetanilide.

12. a-Benzoylacetanilide. 13. 2 -(m benzoylacetamidophenyl) -1 octadecy1-5-benzimidazo1e-sulfonic acid. 25. p-Sulfamylbenzoylacetanilide;

l 25 O4; 0 01120 0 NEG-S OaNHi C so H 26. N,N' 1 -methy1ethy1enebisaceto-acetamide CHaOOOHQCONHCHCH2NHCOCHzCOCHz -c o-omooNH 3o H: 14. o-Acetcacetaniside. ZA'pentanedione 15. 4.4 -methy1enebis-a-benzoy1acetani1ide. CH3COCH2COCH3 O-o 0 omo ONH-QOHr-ONHC 001120 0-6 28. 1.3-dipheny1-1.3-propanedi0ne. 29. Benzoylacetonitrile. 30. Cyanoacetanilide.

31. a-Pheny1su1fonylacetophenone.

16. o-Pheny1acetoacetanilide. 17. 4- 2-pyridylsulfamyl-a-benzoylacetanilide.

18. 5.5-urey1enebis-N-benzoy1acety1 anthrlanilic acid. y1-5-benzimidazole-su1fonic acid.

Go 0 03,0 ONH- -NHC ONE-@NH-C 0 omo o@ I t 0 OH 0 OH 19. 3.3 ureylenebis 6 p-benzoylacetamido- 33. p Cyanoacetyl B octadecenylsuccinalic benzamido-benzene sulfonic acid. acid.

OCOCHQCONHOC ONE? CH2CN 03H NH 0 O0 0 01120 ONH-O-C ONH 111E OaH NH 20. p-Benzoylacetamidobenzoic acid. 0 o11-o m 01120 0 OH O0 0 01120 ONH-O-CO 0H 21. 7 benzoyiacetamido 1 naphthoxyacetic id, couplers in azo dye chemistry. In any case the 0032.430; majority can be made by the interaction of the desired amine with the desired keto ester to yield @430 01116 O-NH the amide.

I The benzimidazole compounds, 1. e., Nos. 13 and 32, are new products. Such compounds are produced, taking compound 32, for example, by

05.0 0 01120 ONH-O-CHz-O-NHCOGHzC OCH:

32. 2 (p-benzoylacetamidophenyl) -1-0ctadec-.

Many of the above keto methylene compounds are well known, and are used, for example, as

.-:heating a mixture of 2- (4'-aminophenyl) -1- octadecylbenzimidazole-5-sulfonic acid, benzoyl acetic ester, and pyridine to a temperature of 1:10 to 120 C. .for about four :hours. The reaction :mixture is then diluted with water and ldnowned in la mixture or .concentrated hydrochloric acid and ice water. The product is :collected on a filter, washed and air dried.

It may be purified by dissolving it in methanol,

:refluxing the solution Lior one-half .hour, cooling (l toroom temperature, andfiltering.

Compound 13 is made .in the same manner excepting that 2--(4' -,aminophenyl)--l-octadecylbenzimidazole--sulfonic acid is replaced by .2- .(3' aminophenyl) -1-octadecylbenzimidazole 5- :sulfonic acid. 1

The parent benzimidazole, -'on the other hand, is prepared byheating a 3-amino-4-alkylamino benzene sulfonic or :carboxylic acid with the -de- {sired nitro benzenecarboxylic acid chloride in the presence ,of pyridine or any .other suitable :acid binding agent. The .nitro group in the benbimidazole is then reduced 'to an amino group. Preparation of the intermediate is analogous to 'the :method described iin .copending application Serial (No. 745,113, filed April 30, 1947, with :the "exception that the l -hydroxy-2enaphthoylchloride is replaced by the desired nitro-benzoyl chloride followed by reduction of thenitro group after ring closure.

.In the processing of color .film by the color forming development method, the general practice :is to bleach the .silver images after acolor development with a bleaching bath havingapH slightly .OIl theacid side. .Furthermore,.inasmuch as .it has been recognized that the cyan and magenta azine dyes are acid-.resistant,it has been proposed in the method employed .for forming .images of such dyes to fix the silver halide after bleaching by means of an acid hardening ifixing bath. This procedure has the advantage that ,it permits hardening of theemulsion :during normal processing .and without theutilization iota separate step .forthis purpose.

It has been the observation of operators that -:the processing of color .film as described above,

while utilizing the aforementioned 2.4-diaminoaniline color developers, and as the color former an open chaink-etomethylene compound, leads to dye images which are magenta rather than :yellow in color. We have now found, .and this constitutes a very important part of .our invento'in, that such a magenta image is converted into a permanent yellow image by subsequent treatment with anlalkali.

The alkali treatment step leading toyellowrdye image formation is conducted before final "washing and drying and involves merely the subjection of the photographic element being processed to the action of @an aqueous solution of a. water rsoluble alkali, such as sodium carbonate, potassium carbonate and the like. As the pH of the photographic elementincreases, the yellow image appears as a result roftthe transformation of the previously formed magenta image.

The particular stage at which the alkali treatment is interposed may varydepending upon the nature of the fixing bath employed. Generally speaking, such alkali treatment will be a final phase of the processing operation and will usually lbelsucceeded by the final wash and drying. This order will always prevail 'where the fixing bath is acidic. If, however, the fixing bath is neutral, then the alkali treatment may follow bleaching and precede fixing. In any case, the

061150 001126 ONHCaH, CHaNH GHSNH; Ring 7 closure SOiH NH O 0115 transient azo-methine intermediate NEG/5H5 yellowdye image It is of course tobeunderstood that the above compound may existin tautomeric form. The yellowdyes thusformed appear to'be true azines. llh us they Withstand treatment with acid bisul- .ifite-ewhereas the 1y6110W azomethines do not. Furthermore, they are not split 'by treatment with dilute solutions of strong mineral acids as happens with the :yellow azomethines.

The process may be carriedrout by utilizing the color formers in the color forming developer or in the silver-halide emulsion. Preferably, however, the color formers are'loca'ted in the emulsion and are so constituted that they do not difluse therefrom .during the photographic processing. The color formers .may be rendered fast to ,dif- ,insion in the emulsions by methods usually employedin the art, for example, those described in Unitedv States Patents Nos. 2,178,612, 2,179,244, 2,179,234, 2,179,238, 2,179,239 ..2,179,3.44, 2,186,045, 32,136,719, 2,186,732, 2,186,733, 2,186,734, 2,186,849, .2,18,6,851 2,186,852 2,200,306, 2,280,722, 2,292,575, 2 .,3ll3;928,.,and 2,307,399. However, the utiliza- ,.tionl-o'f allong .aliphaticchain to render the components .nonemignatory has been found to .give best results. .Examples of compounds containing such non-diffusing groups appear above.

The process may be utilized for the formation "0;? ,negative :color images, positive color images,

1 or of-reversedlcolor images by following the usual .rleyersal ,method, ti e .exposing, developing in black and white, re-exposing, and. color developing with a 2.4-diamino-aniline.

The yellow dye images produced by the present invention have excellent light fastness and brilliance and very adequately complement the magenta and cyan dyes produced by the azine process.

The following examples serve to illustrate the invention, but it is to be understood that the invention is not limited thereto.

Example 1 To 100 ml. of a developer solution made up as follows:

S-phenylamino -4 methylamino metanilic acid grams 8.0 Metol do 1.0 Sodium sulfite 1 do 60.0 Potassium carbonate do 20.0 Potassium bromide do 10.0 Benzylamine d 5.0 Water to "ml." 1000 was added a solution of 0.2 gram of a-benzoylacetanilide dissolved in 4 ml. of ethyl alcohol and 1 ml. of 10% sodium hydroxide solution. A strip of positive film carrying a silver halide image was treated in this developer-color-former solution for 10 minutes at 20 C. with agitation. The strip was then washed for minutes in running water at 18 C. and then bleached in a ferricyanide-bromide bleach until all developed silver was converted into silver bromide. The strip was then washed until free from bleach and then fixed in acid-hypo. At this point the strip carried a reddish-magenta dye image which was an exact duplicate of the original silver halide image.

After the strip had been washed free of hypo it was treated in a 5% solution of sodium carbonate until the reddish-magenta image was completely converted to a brilliant yellow dye image, about 1 minute being required for the conversion. The yellow image so prepared was stable to washing and drying and showed excellent light fastness and brilliance.

Example 2 A photographic silver halide emulsion containing as a non-difiusing color former p-cyanoacetyl-B-octadecenyl-succinalic acid having the following constitution:

is exposed, developed in black and white, re-

in duplicate of the original latent silver halide image. After the strip was washed free of hypo, it was bathed in a 5% sodium carbonate solution for 2 minutes whereupon the magenta image was converted to a yellow dye image.

Example 3 The procedure is the same as in Example 1 excepting that the developer is made up of equal parts of 4.6-di-(phenylamino)-metanilic acid silver halide emulsion in the presence of an open chain keto methylene compound with a 2.4-diamino-aniline in which the nitrogen atoms in 2- and 4-positions have directly linked thereto a carbon atom of a radical selected from the class consisting of aliphatic and aromatic radicals, bleaching and fixing said emulsion, and adjusting the pH of the emulsion in a final phase of the processing operation by treatment with an alkali untilthe yellow image manifests itself when the emulsion has been previously subjected to an acidic treating bath.

2. The process of producing yellow dye images which are resistant to splitting by strong mineral acids, which comprises developing a devolopable silver halide emulsion in the presence of an open chain keto methylene compound with a 2.4-diamino-aniline in which the nitrogen atoms in 2- and 4-positions are directly linked to the carbon atom of a radical selected from the class consisting of aliphatic and aromatic radicals, bleaching the silver formed by such development, fixing the silver salts by an acid hardening fixing bath, and subsequently adjusting the pH of the emulsion by treatment with an alkali until the yellow image manifests itself.

3. The process as defined in claim 1 wherein the open chain keto methylene compound contains a benzoylacet radical.

4. The process as defined in claim 2 wherein the 2.4-diamino-aniline is 6-phenylamino-4- methylamino-metanilic acid and wherein the open chain keto methylene compound is a-benzoylacetanilide.

5. The process as defined in claim 2 wherein the 2.4-diamino-aniline is 6-phenylamino-4- methylamino-metanilic acid and wherein the open chain keto methylene compound is p-cyano-acetyl- 3-octadecenylsuccinalic acid.

6. The process as defined in claim 2 wherein the 2.4-diamino-aniline is composed of a mixture of equal parts of 4.6-di-(phenylamino) -metanilic acid and 4-methylamino-G-phenylamino-metanilic acid and the open chain keto methylene compound is a-benzoylacetanilide.

'7. The process as defined in claim 1 wherein the pH is adjusted by means of a 5% solution of sodium carbonate.

8. The process as defined in claim 2 wherein the pH is adjusted by means of a 5% solution of sodium carbonate.

DONALD E. SARGENT. ROBERT C. GUNTHER.

REFERENCES CITED UNITED STATES PATENTS Name Date Tulagin Jan. 21, 1947 Number 

1. THE PROCESS OF PRODUCING YELLOW DYE IMAGES WHICH ARE RESISTANT TO SPLITTING BY STRONG MINERAL ACIDS, WHICH COMPRISES DEVELOPING A DEVELOPABLE SILVER HALIDE EMULSION IN THE PRESENCE OF AN OPEN CHAIN KETO METHYLENE COMPOUND WITH A 2.4-DIAMINO-ANILINE IN WHICH THE NITROGEN ATOMS IN 2AND 4-POSITIONS HAVE DIRECTLY LINKED THERETO A CARBON ATOM OF A RADICAL SELECTED FROM THE CLASS CONSISTING OF ALIPHATIC AND AROMATIC RADICALS, BLEACHING AND FIXING SAID EMULSION, AND ADJUSTING THE PH OF THE EMULSION IN A FINAL PHASE OF THE PROCESSING OPERATION BY TREATMENT WITH AN ALKALI UNTIL THE YELLOW IMAGE MANIFESTS ITSELF WHEN THE EMULSION HAS BEEN PREVIOUSLY SUBJECTED TO AN ACIDIC TREATING BATH. 